Color photographic photosensitive emulsion and color photographic material

ABSTRACT

In color photographic photosensitive materials, coupler can be stably and finely dispersed in a silver halide color photographic emulsion by addition of a polymer which contains, as side chains in one molecule, carboxyl group, imidazole group and amide group or N-(1,1-dimethyl-3-oxobutyl)aminocarbonyl group beside said three groups.

United States Patent Ueda et al. 1 Sept. 23, 1975 15 COLOR PHOTOGRAPHIC3,598.600 8/1971 Tuites et ,11, 96/114 PHOTOSENSITIVE EMULSION AND g i96/114 ague e a COLOR PHOTOGRAPH: MATERIAL 3.764.327 l0/l973 Nagae et a]96/l I4 [75] Inventors: Bunzo Ueda; Sigeru lguchi; Tetsuo 3.813.2515/1974 Hollister et al. 96/114 Yano; Tamotu Iwata, all of Nagaokakyo'Japan Primary E.raminer-J. Travis Brown [73] Assignee: Mitsubishi PaperMills, Ltd., Japan An Agent, or Fi .c h D rby & 221 Filed: Jan. 25, 1974Cushma [21] App]. No.: 436,790

[57] ABSTRACT [30] Foreign Application Priority Data in colorphotographic photosensitive materials, coum dpdn pler can be stably andfinely dispersed in a silver hal- 152 US. Cl. 96/100- 96/84 96/1 14 idePhomgmphic emulsion by addition of Poly 151 lm. c1. oosc 1/40- oosc 1/72which Side chains in one [58] Field of Search 96/1 14 100 carboxyl groupimidazo'e group and amide gmuP N-(1,l-dimethyl-3-oxobutyl)aminocarbonylgroup be- [56] References Cited side said three groups.

UNITED STATES PATENTS 6/1969 Kondo et al. 96/114 10 Claims, No DrawingsCOLOR PHOTOGRAPHIC PHOTOSENSITIVE EMULSION AND COLOR PHOTOGRAPHICMATERIAL BACKGROUND OF THE INVENTION The present invention relates to acolor photographic photosensitive material. More particularly, itrelates to an inner type color photographic photosensitive material inwhich a color coupler which couples an oxidation product ofN,N-dialkyl-para-phenylenediamine developing agent to form a dye imageis stably dispersed in a silver halide photographic emulsion layer.

Generally, there are two methods for introducing a coupler into a silverhalide photographic emulsion, namely, one method which comprisesintroducing it by adding water soluble or alkali soluble group theretoand the other method which comprises mechanically dispersing a solutionof an oil soluble coupler in solvent of high boiling point in gelatinwith a surface active agent and redispersing thus obtained dispersedsolution in a silver halide emulsion. However, both of these methodshave various defects. According to the former method, when the couplerwhich carries carboxyl group and (or) sulfon group is incorporated intosilver halide gelatin emulsion, generally, said coupler is dissolved ina solution of alkali metal hydroxide such as aqueous sodium hydroxide,alcoholic potassium hydroxide, etc. and then is added to the silverhalide gelatin emulsion. In this case, coagulation may occur. Moreover,addition of a coupler which is soluble in only a highly alkalinesolution causes excessive increase in pH of the photographic emulsionand therefore, it must be made acidic again, due to which coagulationmay also be caused. Furthermore, there are other difficulties caused dueto alcohol used in a large amount for making the dissolving of couplereasier. In addition, there is the problem that viscosity of thephotographic emulsion changes with lapse of time, which appears to beattributable to the reaction of such type of coupler and gelatin.According to the latter method 4 comprising dispersing an oil solublecoupler, there is a difficulty in solubility of the coupler in thesolvents of high boiling point such as dibutyl phthalate, tricresylphosphate, etc. and a large amount of solvent is required. Furthermore,when the coupler is dissolved in only the solvent of high boiling point,particles of the dispersed coupler become coarse to result in reductionin density of colored image and obscuration due to irradiation.Therefore, generally, solvents of low boiling point such as ethylacetate, methylethyl ketone, toluene, benzene, cyclohexane, etc. arejointly used as assistant solvent, but unless the coupler is such one assubstantially improved in solubility, recrystallization occurs andcoloration often becomes insufficient. On the other hand, dispersedparticles of such coupler are preferably as fine as possible. Asdisclosed in The Theory of Photographic Process (Third edition, page386) published from New York Macmillan Company,

in coating (tail-like stripes) occurs due to fine crystals of thecoupler. Furthermore, clogging of filter is caused at filtration beforecoating. Thus, couplers suitable for production of color photographicphotosensitive materials have been extremely limited.

SUMMARY OF THE INVENTION It has now been found that when a syntheticresin which contains, as side chains, imidazole group, amide group andcarboxylic acid group in a same molecule and which is produced bycopolymerization of three vinyl monomers, namely, vinylimidazole,acrylamide and acrylic acid or derivatives thereof or by hydrolyzing acopolymer of the two among said three vinyl monomers or a water solublesynthetic resin produced by introducing N-( l l -dimethyl-3-oxobutyl)aminocarbonyl group is incorporated into a color photographicemulsion of an inner type color photographic photosensitive materials,especially which contains an oil soluble coupler and a solvent of highboiling point, the coupler can be extremely finely dispersed in theemulsion and recrystallization of the coupler can be restrained.

Introduction of N-( l, 1 -dimethyl-3- oxobutyl)aminocarbonyl group canbe accomplished by adding N-( l,l-dimethyl-3-oxobutyl)acrylamide (theso-called diacetone acrylamide) to the monomers before polymerizationand copolymerizing them in accordance with usual method.

DESCRIPTION OF THE PREFERRED EMBODIMENT Optimum proportion of themonomers in the synthetic resin, namely, vinylimidazole derivative,acrylic acid, acrylamide and diacetone acrylamide varies depending uponkinds of coupler to be dispersed, solvent for the coupler and surfaceactive agent.

The stability of the dispersed particles depends on various complicatedfactors and optimum conditions must be obtained in each case, butusually vinylimidazole is 1-20 mol acrylic acid is 1-20 mol acrylamideis 10-98 mol and diacetone acrylamide 0-50 mol Furthermore, isoelectricpoint of the polymer used in the present invention may be freelycontrolled within the range of 3-8.5 by proportion of each monomer.

The polymer used in the present invention may be applied to any kind ofcouplers. Furthermore, it is also effective for dispersing the agentsusually employed in the color photographic photosensitive materials suchas ultraviolet absorbing agents, e.g., Tinuvin ps, Tinuvin 320 andTinuvin 328 (Tradenames for the products of Ciba-Geigy Co.,Switzerland); stain-inhibitors, e.g., 2,5- di-tert-butylhydroquinone,2,o-di-tert-butyl-p-cresol, etc.; and scavenger, e.g.,2,5-di-tert-octylhydroquinone. Furthermore, the layer to which thepolymer is added is not limited to the photosensitive emulsion layer.

The vinylimidazole derivative used in the present invention is such ashaving the following general formula:

(wherein one of R, R, R" and R' is vinyl group and others are hydrogen,alkyl or hydroxyalkyl). Examples of such vinylimidazole arel-vinylimidazole, vinylimidazole, l-vinyl-2-methyl-imidazole, l-vinyl-2-ethyl-imidazole, l-vinyl-2,4-dimethyl-imidazole,lvinyl-2-ethyl-4-methyl-imidazole, l-vinyl-4(or 5)-62-hydroxyethyl-imidazole, l-vinyl-2-B-hydroxyethylimidazole, etc.

The polymer used in the present invention can be added to the emulsionat any stage of dispersing the coupler, blending the emulsion andcoating of the emulsion and most preferably it can be added atdispersing of the coupler.

Since the dispersing conditions are improved by addition of the polymer,amount of solvent used can be reduced and so the film thickness can bedecreased to result in increase in sharpness of image.

There are substantially no differences in effects of the polymer used inthe present invention depending upon its polymerization degree, but apolymerization degree of 500-2000 is suitable in view of easy formationof an aqueous solution and compatibility with gelatin.

Regarding the amount of the polymer added to the photosensitiveemulsion, addition of about 50-60 by weight of gelatin can provide themaximum effect, but it may be added in an amount of less than saidrange. Furthermore, the polymer may also be added to a silver halideemulsion containing no gelatin as disclosed in Japanese PatentPublication No. 756/68. The preferable weight ratio of silverhalide/polymer is l/0.ll/l0.

The polymer used in the present invention is effective for any couplersused in the inner type color photographic photosensitive materials.Furthermore, the polymer has no troubles such as dye absorption, etc.when the photosensitive materials contain halation inhibiting dyes andirradiation inhibiting dyes (such as food red dye No. 2 or food blue dyeNo. 2 as disclosed in US. Pat. No. 2,956,879 or those disclosed inJapanese Patent Publication No. 13,168/68) and has no adverse effects onphotographic characteristics such as sensitivity, fog, preservability,etc.

Any supports to be coated with emulsion such as films, baryta paper,etc. may be used and have no limitation.

Another effect of the present invention is that as shown in thefollowing Examples the coupler dispersion may be prepared from only thepolymer used in the present invention without using gelatin to inhibitdeviation in quality caused by lot of gelatin and to always obtaincoupler dispersions of a constant quality. Furthermore, since thereoccur no deteriorations such as putrefaction and change of qualitycaused by bacteria, a large amount of coupler dispersion can be producedat one time it can be stored in a form of solution. Therefore, anecessary amount of thus stored coupler dispersion can be doled out andincorporated into silver halide photographic emulsion. This is markedlyadvantageous for producing color photographic photosensitive materials.

The following are examples of preparation of the representativecopolymers used in the present invention.

PREPARATION EXAMPLE 1 Liquid (1) 99% Acrylamide1-Vinyl-2-methylimidazole Nitric acid lsopropyl alcohol Water Liquid 2Water To the liquid (2) through which nitrogen was previously andsufficiently passed and which was kept at 70C was added the liquid (1)dropwise in minutes and thereafter this was kept at 70C for another 30minutes. Then, this was treated with 4 ml of 30 methanolic solution ofN-dihydroxyethylaniline at 70C for 30 minutes to decompose the remainingpotassium pe'rsulfate. Seventy-four grams of water containing 5.8 g ofsodium hydroxide was added thereto and this was heated at 70C for 30minutes to hydrolyze a part of amide group and was neutralized with 17 gof 70% nitric acid and then cooled. The resultant resin solution wasadded to methanol or acetone in an amount of 5 times that of thesolution while stirring to precipitate the resin, which was filtered offand vacuum dried.

About 9 mol of side chains of thus obtained polymer was2-methylimidazole, about 10 mol was carboxyl group and the remainder wasacrylamide group.

PREPARATION EXAMPLE 2 99% Acrylamide V l-Vinyl-2-B.hydroxyethylimidazoleAcrylic acid lsopropyl alcohol Water 2 Potassium persulfate The abovemonomer mixed liquid was subjected to polymerization reaction at 70C for2 hours while passing nitrogen therethrough and stirring. Aftercompletion of the reaction, 4 ml of 3 methanolic solution ofN-dihydroxyethylaniline was added thereto and this was heated at 70C forfurther 30 minutes and then cooled. The resin in the resultant resinsolution was precipitated with methanol or acetone and the precipitatewas vacuum dried.

About 15 mol of side chains of thus obtained polymer was2-B.hydroxyethylimidazole, about 8 mol was carboxyl group and theremainder was acrylamide group.

PREPARATION EXAMPLE 3 Liquid (1) Liquid 2 Potassium persulfate WaterPolymerization was carried out under the same conditions as inPreparation Example 1. To the product was added 4.5 g of sodiumhydroxide and 100 ml of water and this was heated at 70C for 30 minutesto hydrolyze a part of amide group and then was neutralized by adding 14g of 7O 7( nitric acid and 130 g of water and cooled.

The resultant polymer had the compositions of about 8 mol of2methylimidazole group, about 7 mol of carboxyl group, about 20 mol ofdiacetone acrylamide and about 65 mol (remainder) of acrylamide group.

PREPARATlON EXAMPLE 4 99: Acrylamide LVinyl-Z-ethylimidazole Diacetoneacrylamide Acrylic acid lsopropyl alcohol Water Potassium pcrsulfateEXAMPLE 1 Synthetic resin of Preparation Example I 6 kg Water 5% Aqueoussolution of di-Z-ethyl-hexyl sulfo succinate l Magenta c0up|er* 4.

Liquid A Liquid 8 Tricresyl phosphate Ethyl acetate 2 l-(2-4.6-trichluruphenyl)3-l A (3-n-pcniadecylphcnoxy )butylIamide-SpyraZolOne The above liquid A was kept at 50C and the liquid Bwas at 60C to sufficiently dissolve the coupler and then they were mixedand the coupler was dispersed with a homoblender for 1 hour. Forcomparison, a coupler dispersion was prepared under the same conditionsas mentioned above except that 6 kg of photographic inert bone gelatinwas substituted for the synthetic resin of Preparation Example 1.One-tenth of each of said dispersions was added to and redispersed ingelatin silver halide photographic emulsion containing 450 g of silverchlorobromide containing the usual green sensitive sensitizing dye and 1kg of gelatin to prepare color photographic emulsions for magenta layer.100 l of 3 gelatin solution was separately prepared. After lapse of 8hours, two layers of the emulsion and the gelatin solution weresimultaneously coated on a baryta paper at 30 m/min by an extrusion typecoaterv State of the tail-like stripes formed after coating of 300 mwere as follows:

Number of the tail-like stripes per in Emulsion of the present invention[0 The comparative emulsion 540 0. lO t 0.45;.1.

Emulsion of the present invention The comparative emulsion l l of eachemulsion was left at 40C for 3 days and then was filtered with a filterfabric of Amilan. in case of the comparative emulsion, the filter fabricwas clogged because the coupler was recrystallized and the filtrationwas impossible while in case of the present emulsion no such troubleswere caused. Thus obtained photosensitive materials were exposed andsubjected to the usual color development treatment comprising colordeveloping, water washing, bleaching with potassiumferricyanide-bromide, fixation, etc. As the result, the photosensitivematerial having the present emulsion produced a brighter magenta imagethan the photosensitive material having the comparative emulsion.

EXAMPLE 2 Example 1 was repeated except that 6 kg of the synthetic resinof Preparation Example 1 was replaced by combination of4 kg of inertgelatin and 2 kg of the synthetic resin of Preparation Example 2 and bycombina tion of 5 kg of inert gelatin and 1 kg of synthetic resin ofPreparation Example 4. Thus obtained two photosensitive materialsyielded the same results as in Example l.

EXAMPLE 3 Synthetic resin of Preparation Liquid A was kept at 50C andliquid B was at C to sufficiently dissolve the ultraviolet ray absorbingagent and then the absorbing agent was dispersed for 1 hour by ahomoblender. For comparison, a dispersion was prepared in the samemanner as mentioned above except that the synthetic resin of PreparationExample 2 was replaced with 86 g of a photographic bone gelatin and thesolvent of high boiling point was increased to 2 times. After thesedispersions were kept at 40C for 24 hours, the state of the dispersionswas observed with a microscope to find that in the comparativedispersion, innumerable crystals of the ultraviolet ray absorbing agentwere produced while in the present dispersion the dispersed particles ofabout 0.1 ,u. were stably maintained. Thus obtained ultraviolet rayabsorbing agent dispersion may be coated on a coupler containingemulsion layer and this can be applied to a color photographicphotosensitive material.

What is claimed is:

l. [n a color photographic silver halide emulsion which comprises silverhalide and a coupler, the improvement of additionally including in saidemulsion a polymer which contains as side chain groups (a) carboxylgroups, (b) imidazole groups, and (c) amide groups or side chain groups(a), (b) and (c) and also ((1) N-(1,1-dimethyl-3-oxobutyl) aminocarbonylgroups, the proportions of said groups being (a) 1-20 mo] (b) 1-20 mol(c) lO-98 mol and ((1) -50 mol said polymer being a terpolymer of l)acrylic acid, (2) acrylamide and (3) a vinyl imidazole or being atetrapolymer of l (2), (3) and also (4) diacetone acrylamide.

2. A color photographic silver halide emulsion according to claim 1,wherein the polymer has a polymerization degree of 500-2000.

3. A color photographic silver halide emulsion according to claim 2,wherein the weight ratio of silver halide/polymer is l/0.ll/l0.

4. A color photographic material which comprises a support and theemulsion as defined in claim 2 coated thereon.

5. An emulsion according to claim 1 wherein the vinyl imidazole has theformula where one of R, R, R and R is the vinyl group and the othermembers of R, R, R" and R are hydrogen, alkyl or hydroxyalkyl.

6. An emulsion according to claim 1 wherein the polymer is a terpolymerof acrylamide, l-vinyl-2-,B- hydroxyethyl-imidazole and acrylic acid.

7. An emulsion according to claim 1 wherein the polymer is a terpolymerprepared by hydrolyzing a copolymer of acrylamide andl-vinyl-2-methylimidazole to form a terpolymer of l-vinyl-2-methylimidazole and acrylic acid.

8. An emulsion according to claim 1 wherein the polymer is atetrapolymer prepared by hydrolyzing a terpolymer of acrylamide,1-vinyl-2-methylimidazole and diacetone acrylamide.

9. An emulsion according to claim 1 wherein the polymer is atetrapolymer of acrylamide, l-vinyl-2- ethylimidazole, diacetoneacrylamide and acrylic acid.

10. A coupler dispersion which comprises a coupler and the polymer asdefined in claim I.

ac rylamide

1. IN A COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES SILVERHALIDE AND A COUPLER, THE IMPROVEMENT OF ADDITIONALLY INCLUDING IN SAIDEMULSION A POLYMER WHICH CONTAINS AS SIDE CHAIN GROUPS (A) CARBOXYLGROUPS, (B) IMIDAZOLE GROUPS, AND (C) AMIDE GROUPS OR SIDE CHAIN GROUPS(A), (B) AND (C) AND ALSO (D) N-(1,1-DIMETHYL-3-OXOBUTYL) AMINOCARBONYLGROUPS, THE PROPORTIONS OF SAID GROUPS BEING (A) 1-20 MOL % (B) 1-20 MOL%, (C) 10-98 MOL % AND (D) 0-50 MOL %, SAID POLYMER BEING A TERPOLYMEROF (1) ACRYLIC ACID, (2) ACRYLAMIDE AND (3) A VINYL IMIDAZOLE OR BEING ATETRAPOLYMER OF (1), (2), (3) AND ALSO (4) DIACETONE ACRYLAMIDE.
 2. Acolor photographic silver halide emulsion according to claim 1, whereinthe polymer has a polymerization degree of 500-2000.
 3. A colorphotographic silver halide emulsion according to claim 2, wherein theweight ratio of silver halide/polymer is 1/0.1-1/10.
 4. A colorphotographic material which comprises a support and the emulsion asdefined in claim 2 coated thereon.
 5. An emulsion according to claim 1wherein the vinyl imidazole has the formula
 6. An emulsion according toclaim 1 wherein the polymer is a terpolymer of acrylamide, 1-vinyl-2-Beta -hydroxyethyl-imidazole and acrylic acid.
 7. An emulsion accordingto claim 1 wherein the polymer is a terpolymer prepared by hydrolyzing acopolymer of acrylamide and 1-vinyl-2-methylimidazole to form aterpolymer of acrylamide, 1-vinyl-2-methylimidazole and acrylic acid. 8.An emulsion according to claim 1 wherein the polymer is a tetrapolymerprepared by hydrolyzing a terpolymer of acrylamide,1-vinyl-2-methylimidazole and diacetone acrylamide.
 9. An emulsionaccording to claim 1 wherein the polymer is a tetrapolymer ofacrylamide, 1-vinyl-2-ethylimidazole, diacetone acrylamide and acrylicacid.
 10. A coupler dispersion which comprises a coupler and the polymeras defined in claim 1.